The present invention relates to a series of derivatives of novel ether diamine compounds prepared by the cyanobutylation reaction of an alcohol having 3 to 22 carbon atoms with 2-pentenenitrile to form a branched alkyl ether nitrile. The alkyl ether nitrites formed by the process are hydrogenated to form alkylether amines. The resulting products are then reacted with 2-pentenenitrile or acrylonitrile and hydrogenated to yield a diamine, which can likewise be derivatized. Specifically, the present invention deals with two types of tertiary amines, one made by the reaction of novel ether diamines compounds with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof producing alkoxylated tertiary diamines and the other conveniently made by the reaction of novel ether diamine compounds with formaldehyde and hydrogen producing methylated tertiary diamines. The invention also discloses novel diamine oxides, and quaternary compounds made from said tertiary amines.
U.S. Pat. Nos. 4,260,556 and 4,211,725 teach reaction of 2-pentenenitrile with ammonia or ethylenediamine to produce alkylaminonitriles. U.S. Pat. No. 4,496,474 teaches the reaction of 2-pentenenitrile with alkylamines having from 8 to 22 carbons to produce the corresponding nitrile compound. U.S. Pat. No. 5,070,202 teaches a process having improved reaction rate and selectivity in the reaction of 2-pentenenitrile with amines to form alkylaminonitriles by the incorporation of from 15 to 60 weight percent water in the reaction mixture. These references do not include the critical ether linkage needed to make the products of the present invention.
U.S. Pat. No. 5,902,883 to Herkes discloses the cyanobutylation of various amines to make diamines. Herkes uses 3-pentenenitrile, 4-pentenenitrile or mixtures of 3-pentenenitrile and 4-pentenenitrile to make his product. This does not result in the desired branching that comes from the compounds of the present invention, nor does it include the critical ether linkage in the molecule. Herkes has done some work with the cyanobutylation of lower molecular weight alcohols (C3 to C8) to form primary amines. These materials lack the hydrophobicity to be good surface-active agents.
It has now been found that by reacting alcohols with 2-pentenenitrile and hydrogenating to the alkyloxypentyl amines, followed by cyonoethylation or cyonobutylation to form diamines, followed by alkoxylation or methylation to form tertiary amines and in a subsequent step derivitization of said tertiary amines results in products with unique properties. Further reaction to form the salts, quaternary salts, or amine oxides also result in products with unique properties. These include (a) superior liquidity of the resulting products, (b) improved surfactant properties and (c) improved solubility. All of these will become clear as one reads the teachings of the present invention.
The present invention relates to a series of derivatives of novel ether diamine compounds prepared by the cyanobutylation reaction of an alcohol having 3 to 22 carbon atoms with 2-pentenenitrile to form a branched alkyl ether nitrile. The alkyl ether nitrites formed by the process are hydrogenated to form alkylether amines. The ether amine compounds may be used as raw materials for the preparation of the derivatives of the current invention which are the topic of application Ser. No. 459,562 filed Dec. 13, 1999, now U.S. Pat. No. 6,114,585 issued September 2000, and application Ser. No. 09/566,505 filed May 8, 2000 incorporated herein by reference. The resulting product can be reacted with 2-pentenenitrile and or acrylonitrile and in a subsequent step, hydrogenated, to yield a diamine. Specifically, the present invention deals with two types of tertiary amines. One made by the reaction of novel ether diamine compounds with ethylene oxide, propylene oxide, butylene oxide or mixtures thereof to produce an alkoxylated tertiary diamine, and the other conveniently made by the reaction of novel ether diamine compounds with formaldehyde and hydrogen to produce a methylated tertiary diamine. The invention also discloses novel amine oxides, amine salts and quaternary compounds made from said tertiary diamines.
The present invention relates to a series of derivatives of novel ether diamine compounds prepared by the cyanobutylation reaction of an alcohol having 3 to 22 carbon atoms with 2-pentenenitrile to form a branched alkyl ether nitrile. The etheraminonitriles formed by the process are hydrogenated to form alkyl ether amines. The resulting product can be reacted with 2-pentenenitrile or acrylonitrile and hydrogenated to yield a diamine. Specifically, the present invention deals with two types of tertiary amines, one made by the reaction of novel ether diamine compounds with ethylene oxide, propylene oxide or butylene oxide or mixtures thereof producing alkoxylated tertiary diamines and the other made by the reaction of novel ether diamine compounds with formaldehyde and hydrogen producing methylated tertiary diamines. The tertiary ether diamines are also converted to amine oxides and quaternaries.
The compounds of the present invention are diamines and derivatives falling into the following classes:
Class 1xe2x80x94A branched ether diamine conforming to the following structure: 
xe2x80x83wherein;
e is 0 or 1;
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms;
R2 is xe2x80x94(CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2CH(CH2CH3)O)cxe2x80x94;
a, b and c are independently integers ranging from 0 to 30; 
d is 1.
Class 2xe2x80x94An alkoxylated tertiary ether diamine conforming to the following structure: 
xe2x80x83wherein,
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms, aryl having 6 to 20 carbon atoms;
R2 is CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2 CH(CH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30, with the provision that a+b+c are a minimum of 0 and a maximum of 60; 
d is 1;
e is 0 or 1
x, y and z are integers ranging from 0 to 30 with the provision that x+y+z is a minimum of 2 and a maximum of 60.
Class 3xe2x80x94An alkoxylated tertiary ether diamine oxide conforming to the following structure: 
xe2x80x83wherein;
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms, aryl having 6 to 20 carbon atoms;
R2 is CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2 CH(CH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30, with the provision that a+b+c are a minimum of 0 and a maximum of 60; 
d is 1;
e is 0 or 1;
x, y and z are integers ranging from 0 to 30 with the provision that x+y+z is a minimum of 2 and a maximum of 60.
Class 4xe2x80x94A trimethyl tertiary ether diamine conforming to the following structure: 
xe2x80x83wherein;
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms, aryl having 6 to 20 carbon atoms;
R2 is xe2x80x94CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2 CH(CH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30, with the provision that a+b+c are a minimum of 0 and a maximum of 60; 
d is 1;
e is 0 or 1.
Class 5xe2x80x94A trimethyl tertiary ether diamine oxide conforming to the following structure: 
xe2x80x83wherein:
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms, aryl having 6 to 20 carbon atoms;
R2 is xe2x80x94(CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2 CH(CH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30, with the provision that a+b+c are a minimum of 0 and a maximum of 60; 
d is 1;
e is 0 or 1.
Class 6xe2x80x94An ether diamine quaternary conforming to the following structure: 
xe2x80x83wherein:
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms;
R2 is xe2x80x94(CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2CHCH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30; 
d is 1;
e is 0 or 1;
R4 and R5 are selected from the group consisting of xe2x80x94CH3 and
xe2x80x94(CH2CH2O)xxe2x80x94(CH2CH(CH3)O)yxe2x80x94(CH2CH(CH2CH3)O)zH
x, y and z are independent integers ranging from 0 to 20, with the provision that x+y+z is greater than or equal to 3;
R6 is selected from the group consisting of xe2x80x94CH3 and xe2x80x94CH2xe2x80x94C6 H5 
M is an appropriate anion needed for charge balance such as Cl, Br, and CH3SO4, etc.
Each of the various classes of compounds has in common the fact that they are derivatives of a penetene nitrile diamine. The preparation of the compounds of the present invention includes the following steps: (1) reaction of an ether amine with pentene nitrile or acrylonitrile followed by (2) hydrogenation of the nitrile to the diamine, followed by (3) reaction with either formaldehyde and hydrogen or alkoxylated to form a tertiary ether diamine then (4) derivatization of the tertiary amine into an amine oxide or quaternary compound.
In a preferred embodiment of the branched ether diamine conforming to the following structure: 
wherein;
e is 0 or 1;
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms;
R2 is CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2CH(CH2CH3)O)cxe2x80x94; a, b and c are independently integers ranging from 0 to 30; 
d is 1;
R1 is C12H25,
a, b and c are each 0, d is 1 and e is 1.
In another preferred embodiment of the branched ether diamine R1 is hydrogenated tallow, a, b and c are each 0, and e is 0.
In still another preferred embodiment of the ether diamine R1 is C12H25, a, b and c are each 0, and e is 0.
In a preferred embodiment of the branched ether diamine, R1 is hydrogenated tallow, a, b and c are each 0, and e is 0.
In a preferred embodiment of the alkoxylated tertiary ether diamine conforming to the following structure: 
wherein;
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms, aryl having 6 to 20 carbon atoms;
R2 is xe2x80x94CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2 CH(CH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30, with the provision that a+b+c are a minimum of 0 and a maximum of 60; 
d is 1;
e is 0 or 1;
x, y and z are integers ranging from 0 to 30 with the provision that x+y+z is a minimum of 2 and a maximum of 60; R1 is C12H25, a, b, and c each 0, x is 5, and e is 1.
In another preferred embodiment of the alkoxylated tertiary ether diamine R1 is C13H27, a is 0, b is 0, c is 30, y is 2, d is 1 and e is 1.
In another preferred embodiment of the alkoxylated tertiary ether diamine R1 is C12H25, a, b, and each 0, x is 5, and e is 0.
In still another preferred embodiment of the alkoxylated tertiary ether diamine R1 is C13H27, a is 0, b is 0, c is 30, y is 2, and e is 0.
A preferred embodiment of the alkoxylated tertiary ether diamine oxide conforming to the following structure: 
wherein;
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms, aryl having 6 to 20 carbon atoms;
R2 is xe2x80x94CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2 CH(CH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30, with the provision that a+b+c are a minimum of 0 and a maximum of 60; 
d is 1;
e is 0 or 1;
x, y and z are integers ranging from 0 to 30 with the provision that x+y+z is a minimum of 2 and a maximum of 60 is when R1 is C10H21, a, b and c are each 0, x is 60, and e is 1.
In another preferred embodiment of the alkoxylated tertiary diamine oxide R1 is C8H17, a is 1, b is 30, c is 2, x is 1 and y is 2, and e is 1.
In another preferred embodiment of the alkoxylated tertiary diamine oxide R1 is C10H21, a, b and c are each 0, x is 60, and e is 0.
In still another preferred embodiment of the alkoxylated tertiary diamine oxide of R1 is C8H17, a is 1, b is 30, c is 2, x is 1 and y is 2, and e is 0.
In a preferred embodiment of the trimethyl tertiary ether diamine conforming to the following structure: 
wherein;
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms, aryl having 6 to 20 carbon atoms;
R2is xe2x80x94CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94CH2 CH(CH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30, with the provision that a+b+c are a minimum of 0 and a maximum of 60; 
d is 1;
e is 0 or 1 is when R1 is C3H7, b is 5, and e is 1.
In another preferred embodiment of the trimethyl tertiary ether diamine R1 is C12H25, a is 30, and e is 1.
In another preferred embodiment of the trimethyl tertiary ether diamine R1 is C3H7, b is 5, and e is 1.
In another preferred embodiment of the trimethyl tertiary ether diamine R1 is C12H25, a is 30, and e is 1.
A preferred embodiment of the trimethyl tertiary ether diamine oxide conforming to the following structure: 
wherein:
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms, aryl having 6 to 20 carbon atoms;
R2 is xe2x80x94(CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94CH2 CH(CH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30, with the provision that a+b+c are a minimum of 0 and a maximum of 60; 
d is 1;
e is 0 or 1 is when R1 is C8H17, a is 1, b is 30, c is 2, and e is 1.
Another preferred embodiment of the trimethyl tertiary ether diamine is when R1 is C10H21, a, b and c are each 0, and e is 0.
In a preferred embodiment of ether diamine quaternary conforming to the following structure: 
wherein:
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms;
R2 is xe2x80x94(CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2CHCH2CH3)O)cxe2x80x94
a, b and c are independent integers ranging from 0 to 30; 
d is 1;
e is 0 or 1
R4 and R5 are selected from the group consisting of xe2x80x94CH3 and
xe2x80x94CH2CH2O)xxe2x80x94(CH2CH(CH3)O)yxe2x80x94(CH2CH(CH2CH3)O)zH
x, y and z are independent integers ranging from 0 to 20, with the provision that x+y+z is greater than or equal to 3;
R6 is selected from the group consisting of xe2x80x94CH3 and xe2x80x94CH2xe2x80x94C6 H5 
M is an appropriate anion needed for charge balance such as Cl, Br, and CH3SO4, is when R1 is hydrogenated tallow, a, b and c are each 0, R4 and R1 and R6 are CH3 and M is Cl, and e is 0.
Another preferred embodiment of the ether diamine quaternary R1 is C3H7, b is 5, R4, R5 and R6 are CH3.
Raw Material Amine Preparation
The ether amine compounds used as raw materials for the preparation of the derivatives of the current invention are the topic of application Ser. No. 459,562 filed Dec. 13, 1999, now U.S. Pat. No. 6,114,585 issued September 2000, and application Ser. No. 09/566,505 filed May 8, 2000 incorporated herein by reference. They conform to the following structure; 
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms,
R2 is xe2x80x94(CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2CH(CH2CH3)O)cxe2x80x94
a, b and c are independently integers ranging from 0 to 30, 
d is 0 or 1.
Class 1: Ether monoamine (d=0)
The ether monoamines conform to the following structure: 
wherein;
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms
R2 is xe2x80x94(CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2CH(CH2CH3)O)cxe2x80x94;
a, b and c are independently integers ranging from 0 to 30, 
d is 0.
Ether diamine (d=1)
Ether diamine compounds of the present invention conform to the following structure: 
e is 0 or 1
R1 is selected from the group consisting of alkyl having 3 to 22 carbon atoms
R2 is xe2x80x94(CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2CH(CH2CH3)O)cxe2x80x94;
a, b and c are independently integers ranging from 0 to 30, 
d is 1.
Raw Materials Alcohols
The alcohols and alcohol alkoxylates used in the manufacture of the products of the present invention are well known in the art and are commercially available from a variety of suppliers. Suppliers of these materials include Shell Chemical Company, Condea-Vista, Exxon Chemical Company, Henkel Corporation and Siltech Corporation.
R1 O R2xe2x80x94H
Where R2 is (CH2CH2O)axe2x80x94(CH2CH(CH3)O)bxe2x80x94(CH2CH(CH2CH3)O)c
Procedure
Preparation of Ether Nitrile (Cyanobutylation)
One mole of base alcohol is charged to a reaction flask and one mole plus approximately 10% excess of the 2-pentenenitrile is placed in an addition flask. Material is heated while stirred to a temperature of about 40xc2x0 C. Base catalyst (KOH) is added based on the total weight of the reactants charged at about a 0.1 to 0.5% or more preferably 0.2-0.3% basis. A nitrogen blanket is applied to the headspace of the reaction vessel and the mixture is stirred for about 15 minutes at 40xc2x0 C. to incorporate the catalyst into the alcohol. Keep the reaction flask headspace blanketed with nitrogen throughout the entire reaction period.
The addition of the 2-pentenenitrile is exothermic. Charge the 2-pentenentrile to the reaction vessel such that the temperature of reaction is maintained at 40-65xc2x0 C., more preferably 45-60xc2x0 C., and most preferably 50-55xc2x0 C. When all of the 2-pentenenitrile has been added let react for 2 hours at 50xc2x0 C. After the 2 hours add an equivalent amount of acid to neutralize the base catalyst. Stir mixture for 15 minutes then filter the 3-alkoxy-3-ethylpropylnitrile to be hydrogenated to remove salts formed on neutralization of the KOH.
Charge the ether nitrile to an autoclave that is capable of operating at pressures up to 600 psig. Charge 2% by weight of Raney(copyright) Nickel (based upon the weight of the alcohol to the vessel). Seal autoclave and start agitation, increase heat to about 80 to 100xc2x0 C. and vacuum strip out any water that may have been introduced during cyanobutylation or from Raney(copyright) nickel. When no more water appears on the condenser of the vacuum set-up, close autoclave and charge hydrogen gas to about 5 psig. Charge ammonia to vessel to about 60 to 70 psig. Increase heat to 135xc2x0 C. and note pressure. Add hydrogen such that about 150 to 200 psig additional pressure is measured on the autoclave pressure gauge. Maintain continuous hydrogen addition in this manner for a period of 4-6 hours, then close the hydrogen inlet valve and note pressure on the pressure gauge.
Turn off heat and cool to about 70xc2x0 C. Carefully, open vent to release pressure and vacuum strip to remove ammonia. Discharge the 3-alkoxy-3ethylpropylamine and filter to remove Raney(copyright) nickel catalyst.